Detergent composition



y 25. 6 I G. "r. REULAND ETAL 3,332,377

DETERGENT COMPOS IT ION Filed June 30, 1966 Graph Showing SudsingSynergism Fig. 1

1 100% Detergni (1) Basic Formulation (Weight Basis 11 IOO% Deierqeni(II) 30% Total Active Detergent HI 100% Deiergeni (III) 8% Ethyl Alcohoi62% Wmer INVENTORS George T. Reulund Todd L. Coward ATTORNEY This is acontinuation-in-part patent application of copending patent applicationSerial No. 524,363, now abandoned, filed December 23, 1965, which is acontinuation-in-part of Serial No. 423,007, filed January 4, 1965,

now abandoned.

This invention relates to a novel detergent composition. In particular,it relates to a light-duty detergent composition, preferably liquid,which embodies a synergistic ternary mixture of surface activecompounds.

The term light-duty is used in the description of this invention in itsusually accepted context, i.e., namely, as a semi-specialty productdesigned for dishwashing and laundering fine fabrics by hand. The termis also used to differentiate between this class of products andheavy-duty laundering products used in standard and automatic washingmachines which substantially depend for their performance on largeamounts of various types of additives United States Patent such assuds-boosters, detergency builders, sequestering agents and otheringredients.

In order for a cleaning product to be effective in lightdutyapplications, it should have the following desirable properties. Such aproduct should act as a wetting agent to solubilize and emulsify greasysoilsand help remove them from soiled articles, especially from soileddishes. The cleaning composition should be able to disperse and suspendthe soil once it is removed from the articles being washed so that thesoil does not 'redeposit on the articles. Moreover, a most importantprerequisite for a light-duty dishwashing composition is the capabilityof rapidly providing a copious amount of stable suds. In applicationssuch as the washing of dishes and fine fabrics, it is important foraesthetic reasons to provide a suds blanket over the surface of thewashing solution. Even more important, the suds layer or blanket shouldbe stable enough in order to last throughout the entire washingoperation. The cleaning capability of a washing solution is generallygauged by the amount of suds present. In addition, the compositionshould perform these functions efficiently over the wide range ofwashing conditions normally encountered in dishwashing and fine fabricwashing processes (Water temperature, water hardness, soil type, soilload, type of fabric, etc.). Special precaution is taken to insure thata dishwashing composition should be mild on the skin even throughrepeated and prolonged exposure. Still further, it is essential thatsuch a composition should provide a physically stable system over a widerange of storage conditions. Economic considerations can also play animportant role in the preparation of these types of compositions.

.Few detergent compositions are known which otter each of the foregoingadvantages. Those which are known are usually prohibitively expensive asa result of the cost of materials involved.

In the pursuit of compositions which oifer all of the advantagesmentioned above, attempts have been made on the one hand to synthesizenew compounds with the necessary characteristics. Other avenues ofapproach have been to combine known detergent compounds in order to tryto discover synergistic mixtures of such compounds. In view of the lackof information in theprior art that can serve as a guide to suchresearch efforts with mixtures of detergents, progress in this area, hasbeen slow. The present invention represents a notable exception sincethe basis for the present invention is a novel synergistic combinationof surface active compounds.

It is an overall object of the present invention therefore to provide alight-duty detergent composition, preferably liquid, which offers theforegoing advantages, and which excels in some of them, especiallysudsing. Thus, it is a primary object of this invention to provide alightduty liquid detergent composition which embodies a synergisticmixture of ,surface active compounds whose performance characteristicsmake it especially valuable as a dishwashing and fine fabric launderingcomposition. It is another object to provide a high-sudsing light-dutyliquid composition which consists essentially of a synergistic mixtureof detergents in an aqueous vehicle. These and other objects of thepresent invention will become apparent from the following description.

FIGURE 1 is a graph presenting data demonstrating the synergisticsudsing'results made possible by the improved light-duty liquiddetergent compositions of the present invention.

It has now been discovered, according to the present invention, that animproved detergent composition especially suitable for dishwashing andfine fabric cleaning applications can be prepared which embodies asynergistic ternary mixture of two anionic detergent materials and onezwitterionic surface active compound. The three ingredients are mixedaccording to critical proportions and percentages. More particularly,the synergistic composi' tiohs of the present invention contain:

Detergent I: From about 12% to about 60% of a Detergent I which is amixture of from about 30% to about of Component A, from about 20% toabout 70% of Component B, and from about 2% to about 15% of Component C,and wherein;

(a) Said Component A is a mixture of double-bond positional isomers ofwater-soluble salts of alkene-l-sulfonic acids containing from about 12to about 16 carbon atoms, said mixture of positional isomers includingabout 10% to about 25% of an alpha-beta unsaturated isomer, about 30% toabout 70% of a beta-gamma unsaturated isomer, about 5% to about 25% of agammadelta unsaturated isomer, and about 5% to about 10% of adelta-epsilon unsaturated isomer,

(b) Said Component B is a mixture of water-soluble salts 1 ofbifunctionally-substituted sulfur-containing saturated aliphaticcompounds containing from about 12 to about 16 carbon atoms, thefunctional units being hydroxy and sulfonateradicals with the sulfonateradical being attached on the terminal carbon and the hydroxyl groupbeing attached to a carbon atom at least two carbon atoms removed fromthe terminal carbon atom; and

(c) said Component C is a mixture comprising from 30- Water-solublesalts of alkene disulfonates containing from about 12 to about 16 carbonatoms, and from about 5% to about 70% Water-soluble salts of hydroxydisulfonates containing from about 12 to about 16 carbon atoms, saidalkene disulfonates containing a sulfonate group attached to a terminalcarbon atom and a second sulfonate group attached to an internal carbonatom not more than about six carbon atoms removed from said terminalcarbon atom, the alkene double bond being distributed between theterminal carbon atom and about the seventh carbon atom, said hydroxydisulfonates being saturated aliphatic compounds having a sulfonateradical attached to a terminal carbon, a second sulfonate group attachedto an internal carbon atom not more than about six carbon atoms removedfrom said terminal carbon atom, and a hydroxy group attached to a carbonatom which .is not more than about four carbon atoms removed from thesite of. attaohme nt of said second sulfonate group; Detergent II: fromabout 6% to about 50% of Detergent II which is an alkali metal sulfuricacid ester of an alkyl ethoxylate containing from about to about 14carbon atoms in the alkyl portion, and from 1 to about 5 moles ofethylene oxide and Detergent III: From about to about 74% of Detergent(III) which is a zwitterionic quaternary ammonium compound selected fromthe group consisting of compounds having the formula I wherein R is analkyl radical containing from about 12 to about 14 carbon atoms, R and Rare each members selected from the group consisting of methyl, ethyl andhydroxyethyl, R is an alkylene radical having from 1 to about 3 carbonatoms, and 2 is a member selected from the group consisting of hydrogenand hydroxyl, and compounds having the formula wherein R is an alkylradical containing from about 12 to about 14 carbon atoms, and R and Rare each members selected from the group consisting of methyl, ethyl,and hydroxyethyl.

A preferred embodiment of the present invention is a detergentcomposition containing from about 18% to about 36% of Detergent I, fromabout 10% to about 36% of Detergent II, and from about 28%, to about 54%of Detergent III.

In a complete liquid detergent formulation, the synergistic ternarymixture is'generally employed in admixture with Water. The activesynergistic mixture comprises from about 10% to about 50% by weight ofthe composition, with the balance of from about 5 0% to about 90% beingwater. The preferred weight percentage range for the synergistic mixturein a liquid formulation is from about to about 40%, with the remaining60% to 80% being water.

Two of the members of the synergistic ternary mixture, Detergent I andDetergent II are anionic surface active materials and the third member,Detergent III, is a zwitterionic compound. According to the presentinvention it is necessary, not only that the preceding enumeratedpercentages be employed, but it is also essential that there be acritical balance between the combined total of the two anionic compoundsand the zwitterionic compound in the complete composition.

Thus, the weight ratio of the combined anionic compounds, Detergent Iand Detergent II, to the zwitterionic compound, Detergent III, must bewithin the range of from about 1:3 to about 6:1, and preferably betweenabout 1:1 to about 2.5: 1.

It is also necessary to maintain a critical weight ratio between each ofthe two anionic members in the synergistic ternary system of the presentinvention. Detergent I and Detergent II, should be employed within aWeight ratio of Detergent I to Detergent II of from about 10:1

to about 1:4 and preferably within a weight ratio of from about 6:1 toabout 1:2.

According to the present invention, if these prescribed weight ratiosare not embodied in the complete composition, the synergistic sudsingproperties are not obtained.

An example of a high-sudsing light-duty liquid detergent compositionembodying the teachings of the present invention is one which comprisesfrom about 10% to about 50% of a synergistic ternary mixture consistingessentially of the following ingredients:

Detergent I: From about 12% to about 60% of a C based Detergent I asdescribed herein;

Detergent II: From about 6% to about 50% of an alkali metal salt of thesulfuric ester of the tri(ethylene oxide) condensate of coconut fattyalcohols; and

Detergent III. From about 15% to about 74% of 3- N,N dimethylN-alkylammonio)-2-hydroxy-propanel-sulfonate, the alkyl .group beingderived from the middle-cut of coconut fatty alcohol,

Permis- Presible ferred Range, Range, Percent Percent CH3(CH2);CH2CH2CH2CH=CHSO3M 10-25 15-22 CHa(CH2) r-CHzCHrCH=CHCHzSOaM- 30-7040-65 OH3(CH;) .CH2CH=CH CH2CH2SOaM 5-25 1020CH3(CH2)XOH=CHCH2CHZCHXSOSM 5-10 7- 9 In the preceding formulas x is aninteger of from about 6 to about 10, preferably about 8 to about 10, andM represents any cation that forms a soluble salt such as alkali metals,e.g., sodium and potassium, and ammonium, and substituted ammoniumcompounds, e.g., trialkylammonium and trialkylolammonium compounds.Specific examples of substituted ammonium compounds aretriethylammonium, trimethylammonium, and triethanolammonium. Others willbe apparent to those skilled in the art. The symbols x and M have thesame meaning throughout the description of the present invention. Therecan also be present minor amounts of other double-bond positionalisomers. This is the case, for example, when the compositionis preparedby the sulfonation of alpha olefins with uncomplexed sulfur trioxide.Such minor amounts, i.e., less than 10% by weight, do not materiallyalter the excellent cleaning and sudsing properties of the detergentcomposition.

Whereas, Component A is a blend or mixture of certain unsaturatedisomeric aliphatic compounds, Component B consists of a mixture ofcertain saturated aliphatic compounds. A minor amount of unsaturationcan be included in this mixture but preponderantly the compounds aresaturated. The 'bifunctionality of these alkane compounds is due to thepresence of a hydroxyl group and a sulfonate radical on the samemolecule. It has been discovered that the sulfonate radical must belocated on the terminal carbon atom. It also has been discovered thatthe situs of the hydroxyl group in the compounds that can compriseComponent B, is an especially important factor. For example, if thehydroxyl group and the sulfonate radical are attached to adjacent carbonatoms, the valuable detergent and sudsing properties of the Component Bcompounds are substantially decreased. This is especially true when thealpha and beta carbons are the two sites of attachment. The criticalstructural arrangement which must exist in order for the compounds to bedetergents, is that Permis- Presible ferred Range, Range, PercentPercent CHQ(CH2) XCH2CHQCH(OH) OH2CHzS03M.. -90 25-75CH3(CHz)XCH2CH(OH)CHzCHzCH2SOaM 10-90 25-75 CHs(CHr) x-CH (OH)CHaUHzCHaCI-IzSOaM--- 10-90 2575 The value for x and M are as previouslyset forth.

Component B can also include minor quantities, less than about 10%, ofcompounds wherein the hydroxyl group is attached elsewhere along thecarbon chain, e.g., on the sixth carbon atom, without materiallyaltering the overall detergent properties of the compositions. However,at least 90% of the hydroxyl radical substitutions must be in the 3, 4,and 5 positions. The 3- and 4-, and S-hy droxy-n-alkyl sulfonatecompounds, illustrated above, however, are preferred ingredients ofComponent B. In this same connection, it has also been noted that abetahydroxy-n-alkyl-sulfonate compound performs unsatisfactorily as adetergent compound. Not only is it not a good sudsing detergent, but ithas been discovered surprisingly that such a compound constitutes anactual load in the present detergency system. For this reason, the levelof such a compound or mixture of beta-hydroxy-nalkyl compounds should beheld to a minimum. It is noted, however, that minor amounts ofbeta-hydroxy-nalkyl sulfonate compounds can be tolerated in the syn.-ergistic compositions of this invention provided that Components A, Band C of Detergent II otherwise contain the essential ingredients hereindescribed in the proportions and percentages specified.

The alkene disulfonates should preferably comprise from about 40% toabout 80% of the highly polar polyfunctionally substituted aliphaticcompounds which make up component C. These alkene disulfonates shouldpreferably contain from about 12 to about 16 carbon atoms. As mentionedabove, one sulfonate group is attached to the terminal carbon atom. Thesecond sulfonate group is attached to an internal carbon atom that isnot more than about six carbon atoms removed from the terminal carbon.In other words, the second sulfonate functional group can be attached tothe second through about the seventh carbon atom. Component C can alsoinclude minor amounts of compounds in which the second sulfonate islocated more internally than the seventh carbon, such as, for example,on the eighth carbon, etc. There is no apparent advantage in havingthese latter compounds present in the composition, however. According toa preferred embodiment, the major portion, that is from about 60% toabout 95% of the alkene disulfonates, should be 1,2 and 1,3disulfonates.

The alkene double bond can be distributed between the terminal carbonand about the seventh carbon atom; such unsaturation includes, forinstance, alpha-beta, betagamma, gamma-delta, delta-epsilon,epsilon-zeta, and zeta-eta unsaturation. Preferably, the double bondshould 6. be distributed between the second to the sixth carbon atom. Itshould be noted that the alkene double bond can be even more internallylocated than between the zeta: eta carbons, but again no apparentadvantage is gained thereby.

Thus, it can be seen that the alkene disulfonates of Component C containthe polyfunctional combination of a double bond and two sulfonate groupsin an important structural relationship. The preferred compounds asingredients of the alkene disulfonate portion of Component C are2-alkene-1,2-disulfonate; 3-alkene-1,2-disulfonate; and4-al-kene-1,2-disulfonate of the 1,2-disulfonate species; and 3-alkene1,3 disulfonate; 4-alkene-1,3-disulfonate; and 5-alkene-1,3-disulfonateof the 1,3 disulfonate species. The alkene group can contain from about12 to about 16 carbon atoms and preferably about 14 to 16 carbon atoms.The sodium and potassium salts of these compounds are preferred.

Examples of alkene disulfonate compounds are. the following in which acarbon chain length of 16 was selected as being representative, havingsulfonate attachment sites of 1,2 and 1,3;

As mentioned above, Component C contains the afore mentioned andillustrated alkene disulfonates. It also conf tains from about 5% toabout and preferably about 20% to about 60%, water-soluble salts ofhydroxy disul fonates containing from about 12 to about 16 carbon atoms.The terminal carbon atom has attached to it one of the sulfonate groups.The second sulfonate group can be attached to an internal carbon atomnot more than about six carbon atoms removed from said terminal carbonatom. The required hydroxy group isattached to a carbon atom which isnot more than about four carbon atoms removed from the site ofattachment of said second sulfonate group.

The preferred sites of attachment for the hydroxy group on the 1,2disulfonate species are the fourth and fifth carbon atoms to yield4-hydroxyalkane-1,2-disulfonates and S-hydroxyalkane-1,2-disulfonates.For the 1,3.- disulfonates the preferred sites of attachment for the hy;droxy group are the fifth and sixth carbon atoms to yieldS-hydroxyalkane-l,3-disulfonates and fi-hydroxyalkane- 1,3-disu1fonates.The alkane hydrocarbons as before are those having about 12 to about 16carbon atoms and preferably about 14 to about 16 carbon atoms. Accordingto a preferred embodiment, the major portion, that is, from about 60% toabout'95% of the hydroxy disulfonates should be 1,2 and 1,3disulfonates.

Thus, for example, the following compounds are contemplated. Again, a 16carbon 1,2 and 1,3 disulfonate compound is presented as beingrepresentative.

It is postulated that a second polar group, as in Components B and C,spaced a critical distance from a terminally attached polar group in adetergent molecule modifies the crystalline lattice structure in such away as to improve markedly the solubility characteristics of thecompound. While this is not known for certain, it is offered as onepossible explanation for the exceptional detergent properties of thecompositions of the present invention.

Detergent I, as described herein, can be prepared in any suitable mannerso long as the above teachings are adhered to. For instance, each of theingredients can be synthesized separately and then mixed according tothe stated proportions. On the other hand, Detergent I, as describedherein, can be prepared by a process described in copending patentapplication Serial No. 516,081, filed December 23, 1965, by AdriaanKessler and Phillip F. Pflaumer.

If is is desired to synthesize separately the individual components ofDetergent I it is possible to do so according to the procedures in thefollowing discussion. Any other suitable methods can be used. The symbolR as used in the following equation represents an aliphatic hydrocarbonradical that would allow for a total of carbon atoms in the moleculebetween about 12 and about 16. The alpha-beta unsaturated sulfonatecontaining aliphatic compounds of Component A can be prepared readily bydehydrochlorinating a 2-chlorosulfonic acid derivative. A farilydetailed discussion of a suitable preparative route appears in anarticle in the Journal of the Chemical Society, 1949, page 46, writtenby J. D. Rose and A. Lambert. The starting step for this synthesis is areaction between a long chain epoxide and sodium bisulfite to produce a2-hydroxy-1-sulfonate derivative of the particular long chain epoxideused. This reaction product is condensed with PCl to prepare theaforementioned 2- c'hlorosulfonic acid derivative which in turn isreacted with sodium carbonate to yield an alpha-beta unsaturatedcompound.

The other preferred double-bond positional isomers of Component A, i.e.,the beta-gamma, gamma-delta, and delta-epsilon can be prepared by thethermal dehydration Hno RCH7CH(OH) CHaCHzSOaNB. T

Similarly a reaction mixture of a gamma-delta and a delta-epsilondouble-bond isomer compound can be prepared by using a4-hydroxysulfonate as a starting material:

RCHzCH=CHCHzCHzSOaNa RCH=CHCH2CHzCHzSOaN3 The foregoing synthesis of thedouble-bond positional isomers follows closely the well knowndehydration of an organic alcohol as is mentioned in such standard textsas Whitmores Organic Chemistry, second edition, pages 39-41.

There is no need to separate the reaction product of the two illustrateddehydration reactions. The reaction product can be formulated directlyinto a detergent com- I position according to the present invention. If,for some reason, it is desired to work with pure ingredients, they canbe separated into pure forms.

The hydroxy sulfonates of Component B, such as the preferred 3-, 4-, andS-hydroxy compounds can be prepared by the free radical addition ofsodium bisulfite to the corresponding 3-, 4-, or S-hydroxy-l-olefin,respectively:

Free Radical Catalyst RCH(OH)CO=CH1 NaHSOa The hydroxy olefin for use asstarting materials in the preceding free radical addition reaction canbe prepared by well known organo-metallic reactions, e.g., involving analdehyde and a Grignard reagent in Which R and R" are organic radicalsand X is a halogen. For example:

A discussion of the conversion of hydroxyolefins produced by precedingEquations a and b to hydroxy sulfonates appears in an article written byJ. Willens, Bulletin of the Chemical Society of Belgium, vol. 64, page427 (1955).

It is to be understood that other hydroxy sulfonates as desired can beprepared by using different Grign-ard reagents in the reaction equationset forth above.

The alkene disulfonates and the hydroxy disulfonates which compriseComponent C may also be prepared separately by any known manner. Forinstance, the hydroxy disulfonates may be prepared by epoxidizing olefinsulfonic acid isomers, and then opening the epoxide ring with sodiumbisulfite by standard reaction techniques. The hydroxy disulfonates maythen be dehydrated by reactions known to those skilled in the art toyield the corresponding isomeric alkene disulfonates.

As mentioned earlier, the Detergent I components should contain fromabout 12 to about 16 carbon atoms. It is preferred, however, to have thecompounds contain from 14 to 16 carbon atoms. It is not necessary thateach of the compounds contain the same number of carbon atoms. Mixturesof different chain lengths within the prescribed ranges can be used. I Y

The following compositions are illustrative of Detergent I according tothe present invention wherein the percentages are by weight and whereinComponents A, B and C total up to 100% of Detergent I. The percentageslisted for each ingredient are by weight of that particular ingredientin Detergent I.

Detergent I can be comprised as follows with a chain length of 16carbons being representative:

Component A: Percent C H CH=CHSO Na C H CH=CHCH SO Na C H CH=CHCH CH SONa C H CH=CHCH CH CH SO Na 6 Total Component A 65 Component B: Percent CH CH(OI-I)CH CH SO Na C H CI-I(OH)CH CH CH SO Na Total Component B 25Component C: Percent C13H27CH C(SO3N3.)CHgSOgNB. 1.0 C1 H CH=CHCH(SONa)CH SO Na 3.0 n zar- =CHCH CH(SO Na)CH SO Na .5 C11H23-CH2-CH =C(SONa)CH CH SO Na .5 C11H23 'CH CH -CH(SO Na)CH CH SO Na .5 C H -CH=CHCH-CH(SO Na)CH CH SO Na .5 C H -CH(OH)-CHg CH(SO Na)CI-I SO Na 1.5 C H-CH(OH)CH -CH -CH(SO Na)CH SO Na 1.5 C H CH(OI-I)-CH .5 C H -CH(OH)CH CH-CH(SO Na)CI-I --CH SO Na .5

Total Component C 10.0

Detergent I as so comprised has excellent detergent and synergisticsudsing properties when mixed with Detergent II and Detergent IIIaccording to the proportions described herein.

Another illustrative example of Detergent I is as follows:

Component A: Percent (3 I'I29(:I'I (:I'IS()3 1a. 9 C 31'1 7CI'ICI'ICI'I2S()g l a C H CH=CHCH CH SO Na C H CH=CHCH CH CH S0 Na 10 TotalComponent A 65 Component B: Percent C H CH(OH)CH CH SO Na C H CH(OH)CHCH CH SO Na 10 C H CH(OH)CH CH CH CH SO Na 3.

Total Component B 23 1 0 Component C: Percent C H CH -CH -CH CH C(SONa)CH (SO Na) 1.0 C oHg -CH(SO Na)-CH SO Na 3.5 C 3H2 1.0 1o 21 2.-CH; a

-CH CH -SO N8. .5 C H CH CH -CH CH -CH- CHSO NE1 .5 C1oH2 -CH2CH2-CH2C.5 C H CH CH -CH OH) -CH CH(SO Na)CH SO Na 3.0 C H -CH CH (OH) CH CHCH(SO Na)-CH SO Na 1.0 C H --CH CH(OH)CH CH(SO Na)CH CH SO Na 1.0

Total Component C 12.0

This Detergent I composition offers excellent detergent properties ofcleaning and synergistic sudsing in admixturewith Detergents II and IIIas described herein.

The following are other illustrative examples of Detergent I with 12, 14and 16 carbon lengths and are referred to as a C -Based Detergent I, a C-Based Detergent I, and a C -Based Detergent I. Hereinafter thesecompositions will be referred to for simplicity by these terms ratherthan reproducing all of the ingredients.

(1) An active detergent composition referred to herein as C -BasedDetergent I, having the following composition, percentages by weight.

(2) A detergent active composition referred to herein as C -BasedDetergent I and having the following composition, percentages being byweight.

Component A: Percent C H CH=CHSO Na C1 H CHCHCH SO Na 3 3 C H CHCHCH CHSO Na$ C H CH=CHCH CH CH SO Na 6 Total Component A "E Component B:Percent C11H23CH(OH) CH2CH2SO3 Nfl C1H21CH(0H)CH2cH2CH2SO3 Na 5 TotalComponent B 25 11 Component C: Percent v C H CH =CHCH(SO Na)CH CH (SONa) 1.5

CH (SO Na) 3.0 C H CH(OH)CH CH(SO Na) CH CH (SO Na) 1.0

Total Component C 10.0

(3) A detergent composition referred to herein as C Based Detergent Iand having the following composition, percentages being by weight. Thiswas the composition of Detergent I employed in the tests describedbelow, the results of which are presented in FIGURE 1.

Component A: Percent C H CH=CHSO N21 C1 H 7CH CHCH2SO Na C H CH=CHCH CHSO Na 13 C1IH23CH CHCH2CHZCHZSO3Na 6 Total Component A 65 Component B:Percent C H CH(OH)CH CH SO Na 20 C H CH(OH)CH CH CH SO Na TotalComponent B 25 Component C: Percent C H CH=CHCH(S0 Na)CH (SO Na) 4.5 nzs :CHCH (SO Na) CH CH (SO Na) 1.5 C H CH(OH)CH CH(SO Na) CH (SO Na) 3.0C11H23CH OH) CH CH SO Na) CH CH (SO Na) 1.0

Total Component C 10.0

The second anionic species Detergent II which can be employed in thepresent invention in critical admixture with the previously describedanionic member Detergent I, is represented by the formula R'(OC H SO M,wherein R represents an alkyl radical containing from about to about 14carbon atoms, preferably about 12, and y ranges from 1 to about 5. Mrepresents any cation which forms a water soluble salt but preferablysodium, potassium, ammonium and substituted ammonium salts.

The long chain aliphatic radical, R, can contain from about 10 to about14 carbon atoms, compounds having mixed chain lengths within this rangecan be used. Thus, the alkyl radical can be derived from a naturalsource such as the middle-cut of distilled coconut fatty alcohol whichconsists of a mixture of various chain lengths be ing approximately 2% C66% C 23% C and 9% C The important requirement is that the compoundsmust have the preponderant chain length within the C C range andpreferably C It is to be understood that minor amounts of compoundswhose carbon chain length is less than 10 and greater than 14 can betolerated without upsetting the desirable synergistic properties. Thecoconut alkyl species described above represents a preferred embodimentof the present invention. These compounds can be characterized as thesulfated product of the reaction between one mole of a higher fattyalcohol containing the requisite number of carbon atoms and 1 to about 5moles of ethylene oxide. The unbalanced equation for the preparativeroute is:

These compounds can also be made by sulfating and neutralizing alkylethoxylates made by reacting an alkyl bromide with sodium glycolate inan excess of an ethylene glycol.

The value for y in the formula RO(CH CH O) is understood to represent anaverage number of ethylene oxide units in the reaction product, and notan absolute value.

Examples of such compounds which can be used in the present inventionare the sodium salt of the sulfuric ester of the tri(ethylene oxide)condensate of a mixture of coconut fatty alcohols; the sodium salt ofthe sulfuric ester of the di(ethylene oxide) condensate of dodecanol,the potassium salt of the sulfuric ester of the tetra (ethylene oxide)condensate of a mixture of coconut fatty alcohols; the sodium salt ofthe sulfuric ester of the mono (ethylene oxide) condensate oftetradecan'ol; the sodium salt of the sulfuric ester of thepenta(ethylene oxide) condensate of coconut fatty alcohols.

Examples of the zwitterionic detergent compound which can be used asDetergent III in admixture with the blend of the two anionic detergentcompounds described above to provide synergistic cleaning and sudsingresults are as follows:

3-(N,N dimethyl N dodecylammonio) 2 hydroxyprop anel -sulfonate 3-(N,Ndimethyl N dodecylammonio) propane lsulfonate 3-(N,N diethyl Ndodecylammonio) 2 hydroxypropane-l-sul-fonate3-(N,N-di(hydroxyethyl)-N-dodecylammonio) 2 hydroxypropane-l-sulfonate3-(N,N-dimethyl N tetradecylammonio) 2 hydroxypropane-l-sulfon ate3-(N,N-diethy1 N tetradecylammonio) 2 hydroxypropane-l-sulfonate3-[N,N-di(hydroxyethyl) N tetradecylammonio] 2hydroxypropane-l-sulfonate 3-(N,N-dimethyl-N-alkylammonio) 2hydroxypropanel-sulfonate, the alkyl group being derived from themiddle-cut of coconut fatty alcohol 2-(N,N-diethyl-N-alkylammonio) 2hydroxypropanel-sulfonate, the alkyl group being derived from themiddle-cut of coconut fatty alcohol 2-(N,N-diethyl-N alkylammonio) 2hydroxyethanel-sulfonate, the alkyl group being derived from themiddle-cut of coconut fatty alcohol 3- [N,N-di (hydroxyethyl-N-alkylammonio] -2 hydroxypropane-l-sulfonate, the alkyl group beingderived from the middle-cut of coconut fatty alcohol4-[N,N-di(hydroxyethyl)-N-alkylammonio]-2 hydroxybutane-l-sulfonate, thealkyl group being derived from the middle-cut of coconut fatty alcoholThe foregoing sulfonate compounds are illustrative of the class ofsultaine compounds which can usefully be employed in the synergisticcompositions of the present invention. These sultaine compoundsrepresent the preferred zwitterionic compounds.

The following zwitterionic compounds are also useful in the presentinvention and, although they are less preferred than the sultaines, theystill provide valuable synergistic sudsing properties in the detergentcompositions described herein.

(N,N dimethyl-N-dodecylammonio)methane carboxylate(N,N-dimethyl-N-tetradecylammonio)methane carboxylate (N,Ndimethyl-Nalkylammonio)methane carboxylate, the alkyl group being derived from themiddle cut of coconut fatty alcohol As noted above in the specificexamples of suitable zwitterionic quaternary ammonium compounds, thelong chain aliphatic radical can be a C (dode'cyl) or C (tetradecyl)radical or alternatively can be derived from a natural source such asthe middle-cut of distilled coconut fatty alcohol which consists of amixture of various chain lengths being approximately 2% C 66% C 23% Cand 9% C Thus, it has been found essential to have the preponder-antchain length be C and C It is to be understood, that minor amounts ofingredients whose chainlength is less than 10 and greater than 14 can betolerated withoutupsetting the desirable properties of the composition.The coconut alkyl species of the zwitterionic quaternary ammoniumcompounds described above are preferred compounds of this type for usein admixture with the anionic detergent according to the presentinvention.

The quaternary ammonium compounds which are useful in terms of thepresent invention can be prepared by any known method. The way in whichthese compounds are prepared forms no part of the present invention. Oneacceptable synthesis route which is described in detail in German Patent1,018,421, comprises reacting an aliphatic tertiary amine such asdodecyldimethyl amine with a propane sultone. A corresponding hydroxycompound such as 3-(N,N-dimethyl-N-dodecylammonio)-2-hydroxypropane-l-sulfonate can be prepared readily by reactingglycerol-monochlorohydrin sulfonic acid with a suitable tertiary aminesuch as dodecyl dimethyl amine. This process is described in GermanPatent 651,733. Use of a coconut alkyl dimethyl amine or tetradecyldimethyl amine will result in the corresponding desired quaternarycompounds. I

The following examples of liquid detergent compositions are given by wayof illustrating the present invention. It is not intended to limit theinvention thereto, for modifications will be readily apparent to thoseskilled in the, art from a careful reading of the preceding andfollowing descriptions. Percentages are all by weight, unless otherwiseindicated.

Example I 18% C -Based Detergent I having the composition given above 6%Sodium salt of the sulfuric ester of the tri(ethylene oxide) condensateof dodecanol 6% 3-(N,N-dimethyl-N-alkyl ammonio) 2hydroxypropane-l-sulfonate, the alkyl radical being derived from themiddle-cut of coconut fatty alcohol 8% Ethyl alcohol 62% Water ExampleII 20% C -Based Detergent I having the composition given above 20%Sodium salt of the sulfuric acid ester of the di(ethylene oxide)condensate of a mixture of coconut fatty alcohols 10%3-(N,N-dimethyl-N-dodecylammonio)-propane 1- sulfonate 10% Ethyl alcohol40% Water Example 111 15% O -Based Detergent I as described above 5%Potassium salt of the sulfuric ester of the tetra(ethylene oxide)condensate of a mixture of tallow fatty alcohols3-(N,N-dimethyl-N-tetradecylammonio) 2 hydroxypropane-l-sulfonate 5%Ethyl alcohol 50% Water Example IV 4% C -Based Detergent I as describedabove 1% Sodium salt of the sulfuric ester of the rnono(ethylene oxide)condensate of tetradecanol 15% 3-[N,N-di(hydroxyethyl)-N-akylammonio]-2hydroxy-propane-l-sulfonate, the alkyl group being derived fromthe-middle-cut of coconut fatty alcohol 80% Water 1 4' Example V 7.5% C-Based Detergent I described above 2.5% Sodium salt of the sulfuricester of penta(ethylene oxide) condensate of hexadecanol 202-(N,N-diethyl-N-dodecylammonio)ethane-1 sulfonate 7% Ethyl alcohol 63%Water Example VI 14% C -Based Detergent I as described above 6% Sodiumsalt of the sulfuric ester of tri(ethylene oxide) condensate ofdodecanol 20% 3-(N,N-dimethyl-N-dodecylammonio)-propane lsulfonate 60%Water Example VII 6.6% C -Based Detergent I as described above 6.6%Potassium salt of the sulfuric ester of tri(ethylene oxide) condensateof dodecanol 6.6% 4-(N,N-dimethyl-N-tetradecylammonio) 2hydroxypropane-l-sulfonate 802% Water Example VIII 7.5 C -BasedDetergent I as described above 15 Potassium salt of the sulfuric esterof di(ethylene oxide) condensate of a mixture of coconut fatty alcohol-s7.5% 3-(N,N-dimethyl-tetradecylammonio)-2 hydroxypropane-l-sulfonate 70%Water Example IX 8% C -Based Detergent I as described above 24% Sodiumsalt of the sulfuric ester of the tri(ethylene oxide) condensate ofdodecanol 8% 3-(N,N-diethyl-N-tetradecyl amomnio)-2hydroxypr'opane-l-sulfonate 60% Water Example X 4% G -Based Detergent Ias described above 16% The potassium salt of the sulfuric ester of thetetra (ethylene oxide) condensate of a mixture of coconut fatty alcohols5% 3-[N,N-di(hydroxyethyl)-N tetradecyl amomnio] propane-l-sulfonate 8%Ethyl alcohol 67% Water Example XI 15% C -Based Detergent I as describedabove 15% Sodium salt of the sulfuric ester of tri(ethylene oxide)condensate of dodecanol 5% 3-(N,N-dimethyl-N-tetradecylammonio)-Z-hydroxypropane-l-sulfonate 65% Water Each of the precedingexamples provide excellent dishwashing and fine fabric launderingcompositions which have remarkably hig-h-sudsing and cleaningproperties.

While liquid detergent compositions are the preferred embodiment of thepresent invention, solid forms, e.g. granular products, can also beprepared. Such solid particulate products having synergistic sudsingproperties have the following compositions.

Example XII 3% C -Based Detergent I :as described above 3%Sodium salt ofthe sulfuric ester of tri(ethylene oxide) condensate of a mixture ofcoconut fatty alcohols 3 3 (N,N-dimethyl-N-tetradecylammonio-2-hydroxypropane-l-sulfonate 91% Sodium sulfate 1 5 Example XIII 8% C-Based Detergent I as described above 16% Sodium salt of the sulfuricester of the tri(ethylene oxide) condensate of dedecanol 8%3-[N,N-di(hydroxyethyl)-N tetradecyl ammonio]- propane-l-sulfonate 68%Sodium sulfate Example XIV This is an example of a liquid dishwashingcomposition that besides offering synergistic sudsing is outstandinglymild to the skin.

18% C -Based Detergent I as described above 4.5% Sodium salt of thesulfuric ester of the tri(ethylene oxide) condensate of middle-cutcoconut fatty alcohol 7.5% (N,N-dimethyl-N-dodecylammonio)methanecarboxylate 70% Water The following standardized liquid formulation wasused to demonstrate the synergistic properties of the novel ternarymixtures of the present invention. Percentages are by weight.

Percent Total active detergent 30 Ethyl alcohol 8 Water 62 Totalstandardized formulation 100 The ethyl alcohol was used as a solubilizerand a viscosity control measure. Although ethyl alcohol is usuallyemployed in liquid detergent formulations as a solvent to reduceviscosity and to lower the chill temperature, its .use herein is notconsidered essential to the present invention. Its presence has nosubstantial bearing on the sudsing properties of the compositions.

Several compositions were tested using the procedure outlined below. Thecompositions differed from each other only in the make up of the activedetergent portion. Each of the members of the ternary system were testedas the sole detergent active in a formulation. Then, each of the threepossibly binary systems were also evaluated. Thereafter, ternarymixtures were evaluated in which different percentage levels of each ofthe three ingredients were used. The results for each composition testedwere plotted 0n the triangular graph, presented as FIGURE 1, and thepoints were then connected by graph lines. The triangular diagram is ofthe conventional type with each corner representing 100% of one of thethree necessary active detergents of the present invention as indicatedas FIG- URE 1. The straight lines on the diagram each represent byweight. In this manner it was possible to delimit the areas in whichsynergistic sudsing results were obtained.

The procedure used to discover the synergistic mixtures of the presentinvention is a standardized procedure which is performed in thefollowing manner.

A dishpan was prepared containing one gallon of water with a hardness of7 grains, a temperature of 115 F. and a pH of 7. To this solution wasadded 7.25 cc. of the detergent compositions being tested. The solutioncontaining the detergent composition was mechanically agitated and themaximum suds level was measured. This was referred to as the originalsuds level.

After this original suds level was obtained, a series of five ordinarydinner plates soiled with about 2 grams of standardized fatty soil (atriglyceride shortening) were washed in the prepared test solution. Thesuds height was again measured. The procedure was repeated a fixednumber of times. A measurement of the suds height was taken after eachset of five dishes were washed. An average was then obtained for theseveral suds height measurements, and the average was then expressed interms of a percent of the original suds height. This percentage figurerepresents a relative measure of the initial suds volume produced andeven more important, of the stability of the suds formed by eachcomposition in the presence of increasing soil load. The results aredependable and reproducible. Those skilled in performing this evaluationknow from experience that a difference in suds height of from about 3%to about 5% is considered significant.

The results of these evaluations are presented in FIG- URE 1. Thedetergent used as Detergent I was that referred to above as C -basedDetergent I.

The detergent used as Detergent II was the sodium salt of the sulfuricester of the tri(ethylene oxide) condensate of a mixture of coconutfatty alcohols.

The detergent used as Detergent III was 3-(N,N-dimethyl N alkylammonio)2 hydroxypropane 1- sulfonate, the alkyl group being derived from themiddlecut of coconut fatty alcohols.

It will be seen from FIGURE 1 that when each of the members of theternary system are used as the sole active,

average sudsing performance figures were less than 40% in the instanceof Detergent I, and 35% in the instance of Detergent II and DetergentIII. For a binary mixture of Detergents I and II, the highest averagevalues were between 40% and 45%; a binary mixture of Detergents I andIII gave highest average values between 35% and 40%; and a binarymixture of Detergents II and III resulted in highest average valuesbetween 40% and 45 On the other hand, the synergistic ternarycompositions of the present invention were those which fell into thesuperior performance areas designated within the 45% closed graph line.The preferred embodiments of the present invention are those synergisticternary mixtures which are included in the area enclosed by the 50%graph line, approximately in the center of the triangular graph.

It should be noted that the performance results in FIGURE 1 wereobtained with a C based Detergent I. With a different chain length,e.g., 12 or 14 carbon atoms, the graph lines can be expected to deviateslightly from those in FIGURE 1. In any event, however;

when the three detergents are mixed according to the proportions andratios described herein synergistic performance results are obtained andthe advantages of the present invention can be utilized.

The synergistic active detergent compositions of the present inventionalso can be used with other materials to form detergent compositions,particularly light-duty liquid compositions, Such complete compositioncan contain from about 5% to 50% of the detergent mixtures of thisinvention with the remaining 50% to being made up of water solubleinorganic alkaline builder salts, organic sequestering agents, ormixtures thereof, hydro tropes, solubilizing agents, anti-tarnishingagents and water.

The builders and sequestrants are employed at levels of from about 4% toabout 30% and preferably from about 8% to about 25%. Water solubleinorganic alkaline builder salts which can *be used alone or inadmixture are alkali metal carbonates, borates, phosphates,-polyphosphate, bicarbonates and silicates. Specific examples of suchsalts are sodium and potassium, tripolyphosphate, sodium and potassiumcarbonate, sodium and potassium tetraborate, sodium and potasiumpyrophosphate, sodium bicarbonate, sodium hexametaphosphate, sodium,sesequicarbonate, sodium monoand diorthophosphate and potassiumbicarbonate. Such inorganic builder salts.

monium or substituted ammonium, aminopolycarboxylates, e.g., sodium andpotassium N-(Z-hydroxyethyD- ethylenediamine triacetates, sodium andpotassium nitrilotriacetates and sodium, and potassium andtriethanolammonium N-(2-hydroxyethyl)-nitrilodiacetates. Mixed salts ofthese polycarboxylates are also suitable. Other valuable polycarboxylatebuilder compounds are the sodium and potassium salts of polymaleate,polyitaconate and polya-crylate. The alkali metal salts of phytic acid,e.g., sodium phytate, are also suitable as organic alkaline buildersalts (see U.S. Patent 2,739,942).

Polyphosphonates are also valuable builders in terms of the presentinvention including specifically sodium and potassium salts ofethane-l-hydroxy-1,1-diphosphonate,

sodium and potassium salts of methylene diphosphonate, sodium andpotassium salts of ethylene diphosphonate, and sodium and potassiumsalts of ethane-1,1,2-triphosphonate. Other examples include the alkalimetal salts of ethane-Z-carboxy-l,l-diphosphonic acid,hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-lhydroxy-1,1,2 triphosphonic acid, ethane-Z-hydroxy-l,1,2-triphosphonicacid, propane-1,l,3,3-tetraphosphonic acid,propane-1,1,2,3-tetraphosphonic acid, andpropane-1,2,2,3-tetraphosphonic acid.

Hydrotropes can be added if desired to increase the compatibility of theingredients of the formulations of this invention in lightly builtsystems. Preferred hydrotrope anions are benzene sulfonate, xylenesulfonate, and toluene sulfonate. They are preferably use-d as theirsoluble salts such as: ethanol-ammonium, diethanolammonium, andtriethanol-ammonium, and especially as the alkali metal, potassium, orsodium salts. Sodium or potassium toluene sulfonate is especiallypreferred. The hydrotrope is added at levels of from about to about 10%.Levels of from about 2% to 8% are preferred. The upper limit of'about10% is set by increasing dilution of the product by an ingredientsubstantially inert so far as sudsing and detergency are concerned. Thelower limit is the amount required to achieve a homogeneous solution. Itwill be appreciated that it is necessary that the formulations of thisinvention should be liquid at somewhat higher and at somewhat lowertemperatures than usual room temperature. The amount of hydrotrope saltused is preferably the minimum amount which will hold the ingredients insolution at the temper-ature to which it is desired that the formula canbe cooled without phase separation.

As mentioned previously solubilizing agents also can be added, ifnecessary, and those preferred are lower alcohols such as methyl, ethyland propyl alcohols. They are generally employed ata level of from about0% to about 25 by weight of the composition and preferably between aboutto 15% by weight.

Various minor ingredients can also be added to the compositions of thepresent. invention. Such normal and desirable additives includeperfumes, viscosity control agents, opacifiers, and pigments. Inaddition, inert materials such as water-soluble inorganic salts can alsobe present in minor amounts, generally as impurities from the variousingredients or as opacifier stabilizers. For example, ethylene glycoldistearate or polystyrene can be used as opacifiers in amounts of up to3% by weight of the composition.

While liquid detergent compositions represent a preferred embodiment ofthe present invention, the synergistic compositions can also be embodiedin other forms including solids such as granules, flakes, powders andother particulate materials. Such compositions can be prepared aslightly built, medium built or heavily built detergent compositionsusing the builder compounds described herein or equivalents thereof.

While the synergistic ternary detergent composition described hereinfinds special application in so-called light duty or lightly builtdetergent compositions, it can also be used in heavily built liquid andsolid detergent compositions where it is desired to take advantage ofthe synergistic sudsing properties of mixtures described herein. Anexample of such acomposition contains about 17.5% of the novel ternarymixture of the present invention, about 50% of sodium tripolyphosphate,about 24% sodium sulfate and about 8.5% sodium silicate.

It has also been discovered that the synergistic sudsing properties ofthe novel ternary detergent composition described herein can be evenfurther enhanced by adding to said composition from about 0.1% toabout-0.3% by weight of a water hardness salt suchas magnesium sulfate,magnesium chloride, calcium sulfate and calcium chloride, or mixturesthereof. Other well known water hardness salts can also be used such asiron salts and the like. Preferably from about 0.15%- to 0.25% by weightof the inorganic salt should be present in the product. j

The suds building effect is more pronounced in relatively soft water butit is also effective in so-called medium hard water or hard water. Asurprising aspect of this discovery is that the marked improvement insudsing is not obtained-if theequivalentamount ofwater hardness salts isadded to the water solution instead of being present in the detergentproduct.

It should be understood that the foregoing detailed description andspecific examples, while indicating general and preferred embodiments ofthe present invention, are given by way of illustration onlysince-warious changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

What is claimed'is:

1. A synergistic ternary detergent composition consisting essentially ofthe following ingredients:

(I) from about 12% to about 60% of a Detergent I which is a mixture offrom about 30% to about 70% of Component A, from about 20% to about 70%of Component B, and from about 2% to about 15%-of Component C, wherein:

(a) said Component A is a mixture of double-bond positional isomers ofwater soluble salts of alkene-l-sulfonic acids containing from about 12to about 16 carbon atoms, said mixture of positional isomers includingabout 10% to about 25% of an alpha-beta unsaturated isomenabout 30% toabout 70% of a beta-gamma unsaturated isomer, about 5% to about 25 of agammadelta unsaturated isomer, and about 5% to about 10% of adelta-epsilon unsaturated isomer;

(b) said Component B is a mixture of water s-oluble salts ofbifunctionally-substituted sulfurcontaining saturated aliphaticcompounds containing from about 12 to about 16 carbon atoms, thefunctional units being hydroxy and sulfonate radicals with the sulfonateradical always being on the terminal carbon and the hydroxyl radicalbeing attached to a carbon atom at least two carbon atoms removed fromthe terminal carbon atom, at least of the hydroxyl radical substitutionsbeing in the 3, 4 and 5 positions; and

(c) said Component C is a mixture comprising from 30-95% water-solublesalts of alkene di-' sulfonate containing from about 12 to about 16carbon atoms, and from about 5%. to about 70% water-soluble salts ofhydroxy disulfonates containing from about 12 to about 16 carbon atoms,said alkene disulfonates containing a sulfonate group attached to aterminal carbon atom and a second sulfonate group attached to aninternal carbon atom not more than about six carbon atoms removed fromsaid terminal carbon atom, the alkene double bond being distributedbetween the terminal carbon atom and about the seventh carbon atom, saidhydroxy disulfonates being saturated aliphatic compounds having-asulfonate radicabattached to,'a terminal carbon, a second sulfonategroupattached to an internal carbon atom not more than about six carbon atomsremoved from said terminal carbon atom, and a hydroxy group attached toa carbon atom which is not more than about four carbon atoms removedfrom the site of attachment of said second sulfonate group; (II) fromabout 6% to about 50% of Detergent II which is an alkali metal sulfuricacid ester of an alkyl ethoxylate containing from about to about "-14carbon atoms in the alkyl portion, and from 1 to about 5 moles ofethylene oxide; and (III) from about to about 74% of Detergent III whichis a zwitterionic quaternary ammonium compound selected from the groupconsisting of com: pounds having the formula RE; i I

R3 Z I. wherein R is an alkyl radical containing from about 12 to about14 carbon atoms, R and R are each members selected from the groupconsisting of methyl, ethyl and hydroxyethyl, R is an alkylene radicalhaving from 1 to about 3 carbon atoms, and Z is a member selected fromthe group consisting of hydrogen and hydroxyl; and compounds having theformula RiI I-oH2o 0 0- lie wherein R is an alkyl radical containingfrom about 12 to about 14 carbon atoms and R and R are each membersselected from the group consisting of methyl, ethyl and hydroxy ethyl;wherein the combined weightratio of Detergent I plus Detergent II toDetergent III is within the range of from about 1:3 to about 6:1 andwherein the ratio, by weight, of Detergent I to Detergent II is fromabout 10:1 to about 1:4.

2. The synergistic ternary detergent composition of claim 1 whereinDetergents I, II, and III are present in the following percentages: fromabout 18% to about 36% of Detergent I; from about 10% to about 36% ofDetergent II; and from about 28% to about, 54% of Detergent III, whereinthe combined weight ratio of Detergent I plus Detergent II to DetergentIII is within the range of from about 1:1 to about 2.521 and wherein theratio, by weight, of Detergent I to Detergent II is from about 6:1 toabout 1:2.

3. A high-sudsing light-duty liquid detergent composition consistingessentially of from about 10% to about 50% by Weight of the synergisticternary mixture of claim 1 and from about 50% to about 90% water.

4. A high-sudsing light-duty liquid detergent composition comprisingessentially of from about to about 40% by weight of the synergisticternary mixture of claim 1 and from about 60% to about 80% water.

5. A high-sudsing light-duty liquid detergent composition comprisingfrom about 10% to about 50% of a synergistic ternary mixture consistingessentially of the following ingredients:

Detergent I: from about 12% to about 60% of a C -based Detergent I whichis a mixture of from about 30% to about 70% of Component A, from about20% to about 70% of Component B, and from about 2% to about 15% ofComponent C, wherein:

(a) said Component A is a mixture of doublebond positional isomers ofwater soluble salts of alkene-l-sulfonic acids containing 14 carbonatoms, said mixture of positional isomers including about 10% to aboutof an alpha-beta unsaturated isomer, about to about 70% of a beta-gammaunsaturated isomer, about 5% to about 25% of a gamma-delta unsaturatedisomer, and about 5% to about 10% of a deltaepsilon unsaturated isomer;

(b) said Component B is a mixture of water soluble salts ofbifunctionally-substituted sulfur-containing saturated aliphaticcompounds containing 14 carbon atoms, the functional units being hydroxyand sulfonate radicals with the sulfonate radical always being on theterminal carbon and the hydroxyl radical being attached to a carbon atomat least two carbon atoms removed from the terminal carbon atom; and

(c) said Component C is a mixture comprising from 3095% water-solublesalts of alkene disulfonate containing 14 carbon atoms, and from about5% to about 70% water-soluble salts of hydroxy disulfonates containing14 carbon atoms, said alkene disulfonates containing a sulfonate groupattached to a terminal carbon atom and a second sulfonate group attachedto an internal carbon atom not more than about six carbon atoms removedfrom said terminal carbon atom, the alkene double bond being distributedbetween the terminal carbon atom and about the seventh carbon atom, saidhydroxy disulfonates being saturated aliphatic compounds having asulfonate radical attached to a terminal carbon, a second sulfonategroup attached to an internal carbon atom not more than about six carbonatoms removed from said terminal carbon atom, and a hydroxy groupattached to a carbon atom which is not more than about four carbon atomsremoved from the site of attachment of said second sulfonate group;

Detergent II: from about 6% to about 50% of an alkali metal salt of thesulfuric ester of the tri ethylene oxide) condensate of coconut fattyalcohols; and

Detergent III: from about 15 to about 74% of 3(N,N-dimethyl-N-alkylammonio) 2 hydroxypropane-l-sulfonate, the alkylgroup being derived from the middle-cut of coconut fatty alcohol,wherein the combin ed weight ratio of Deteregnt I plus Detergent II toDetergent III is within the range of from about 1:3 to about 6: 1, andwherein the ratio, by weight, of Detergent I to Detergent II is fromabout 10:1 to about 1:4; and'50% to water.

6. A high-sudsing light-duty liquid detergent composition according toclaim 5, containing from about 20% to about 40% of the synergisticternary mixture.

7, A high-sudsing light-duty liquid detergent composition according toclaim 5 wherein the combined weight ratio of Detergent I plus DetergentII to Detergent III is within the range of from about 1:1 to about 25:1and wherein the ratio, by weight, of Detergent I to Detergent II is fromabout 6:1 to about 1:2.

8. A synergistic ternary detergent composition according to claim 1which also contains from about 0.1% to about 0.3% by weight of a waterhardness salt selected from the group consisting of magnesium sulfate,magnesium chloride, calcium sulfate and calcium chloride.

9. A synergistic ternary detergent composition according to claim 8,wherein the Water hardness salt is present at a percentage of from about0.15% to about 0.25% by weight.

References Cited UNITED STATES PATENTS 2,061,617 11/1936 Downing et al.2,061,618 11/19-36 Downing et al. 2,061,620 Il/ 1936 Downing et al.2,477,383 7/1949 Lewis. 3,072,618 1/1963 Turbak.

(Other references on following page) 21 FOREIGN PATENTS 651,783 8/1964Belgium.

OTHER REFERENCES Alpha-Olefine in the surfactant Industry, J. Amer. OilChem. Society November 1963T. H. Liddicoet; 631- 636.

Aikene Sulfonates Made by New Method-Chemical and Engineering News Apr.15, 1963, R. F. Turbak, pp. 96-98.

The Reactions of Sulfur Trioxido and of Its Adducts with OrganicCompounds, Chemical Review 62, #6, December 1962, pp. 549-589.

Chem. Ber., 97, #10, 2903-13 October Molecular Aliphatic Sulfonic Acids.I. 2-HydroXy-1-n-alkanesulfonic Acids, F. Puschel and Claus Kaiser.

Chem. Ber. 97, #10, 2916-25 October 1964, Higher Molecular AliphaticSulfonic Acids. II 3-Hydroxy-1-n Alkanesulfonic Acids and Their InnerEsters (1,3-Sultones), F. Puschel and Claus Kaiser.

Chem. Ber. 97, #10, 2926-33 October 1964, Higher Molecular UnsaturatedSulfonic Acids and the Hydrolysis of 1,3-Alkanesu1tones, F. Puschel andClaus Kaiser.

Chem. Ber. 98, 735-742 1965, Higher Molecular Aliphatic Sulfonic Acids.IV. Sulfonation of Unbranched Alpha-Olefins with S0 F. Puschel and ClausKaiser.

LEON D. ROSDOL, Primary Examiner.

1964, Higher 15 S. E. DARDEN, Assistant Examiner.

1. A SYNERGISTIC TERNARY DETERGENT COMPOSITION CONSISTING ESSENTIALLY OFTHE FOLLOWING INGREDIENTS: (I) FROM ABOUT 12% TO ABOUT 60% OF ADETERGENT I WHICH IS A MIXTURE OF FROM ABOUT 30% TO ABOUT 70% OFCOMPONENT A, FROM ABOUT 20% TO ABOUT 70% OF COMPONENT B, AND FROM ABOUT2% TO ABOUT 15% OF COMPONENT C, WHEREIN: (A) SAID COMPONENT A IS AMIXTURE OF DOUBLE-BOND POSITIONAL ISOMERS OF WATER SOLUBLE SALTS OFALKENE-1-SULFONIC ACIDS CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBONATOMS, SAID MIXTURE OF POSITIONAL ISOMERS INCLUDING ABOUT 10% TO ABOUT25% OF AN ALPHA-BETA UNSATURATED ISOMER, ABOUT 30% TO ABOUT 70% OF ABETA-GAMMA UNSATURATED ISOMER, ABOUT 5% TO ABOUT 25% OF A GAMMADELTAUNSATURATED ISOMER, AND ABOUT 5% TO ABOUT 10% OF A DELTA-EPSILONUNSATURATED ISOMER; (B) SAID COMPONENT B IS A MIXTURE OF WATER SOLUBLESALTS OF BIFUNCTIONALLY-SUBSTITUTED SULFURCONTAINING SATURATED ALIPHATICCOMPOUNDS CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, THEFUNCTIONAL UNITES BEING HYDROXY AND SULFONATE RADICALS WITH THESULFONATE RADICAL ALWAYS BEING ON THE TERMINAL CARBON AND THE HYDROXYLRADICAL BEING ATTACHED TO A CARBON ATOM AT LEAST TWO CARBON ATOMSREMOVED FROM THE TEMRINAL CARBON ATOM, AT LEAST 90% OF THE HYDROXYRADICAL SUBSTITUTIONS BEING IN THE 3, 4 AND 5 POSITIONS; AND (C) SAIDCOMPONENT C IS A MIXTURE COMPRISING FROM 30-95% WATER-SOLUBL SALTS OFALKENE DISULFONATE CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS,AND FROM ABOUT 5% TO ABOUT 70% WATER-SOLUBLE SALTS OF HYDROXYDISFULFONATES CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, SAIDALKENE DISULFAONTES CONTAINING A SULFONATE GROUP ATTACHD TO A TERMINALCARBON ATOM AND A SECOND SULFONATE GROUP ATTACHED TO AN INTERNAL CARBONATOM NOT MORE THAN ABOUT SIX CARBON ATOMS REMOVED FROM SAID TERMINALCARBON ATOM, THE ALKENE DOUBLE BOND BEING DISTRIBUTED BETWEEN THETERMINAL CARBON ATOMS AND ABOUT THE SEVENTH CARBON ATOM, SAID HYDROXYDISULFONATES BEING SATURATED ALIPHATIC COMPOUNDS HAVING A SULFONATERADICAL ATTACHED TO A TERMINAL CARBON, A SECOND SULFONATE GROUP ATTACHEDTO AN INTERNAL CARBON ATOM NOT MORE THAN ABOUT SIX CARBON ATOMS REMOVEDFROM SAID TERMINAL CARBON ATOM, AND A HYDROXY GROUP ATTACHED TO A CARBONATOM WHICH IS NOT MORE THAN ABOUT FOUR CARBON ATOMS REMOVED FROM THESITE OF ATTACHMENT OF SAID SECOND SULFONATE GROUP; (II) FROM ABOUT 6% TOABOUT 50% OF DETERGENT II WHICH IS AN ALKALI METAL SULFURIC ACID ESTEROF AN ALKYL ETHOXYLATE CONTAINING FROM ABOUT 10 TO ABOUT 14 CARBON ATOMSIN THE ALKYL PORTION, AND FROM 1 TO ABOUT 5 MOLES OF EHTYLENE OXIDE; AND(III) FROM ABOUT 15% TO ABOUT 74% OF DETERGENT III WHICH IS AZWITTERIONIC AUATERNARY AMMONIUM COMPOUND SELECTED FROM THE GROUPCONSISTING OF COMPOUNDS HAVING THE FORMULA